DE1295511B - Process for coloring products which simultaneously contain at least one component with basic groups and at least one component with acidic groups - Google Patents

Description

The present invention relates to a method of coloring in real Solution of products that simultaneously contain at least one component with basic Contain groups and at least one component with acidic groups, and in particular of textile products using at least one dye with anionic Character and at least one dye with a cationic character that thereby is characterized in that the dyeing in an aqueous bath at a pH between 2 and 6 at a temperature of at least 100 ° C simultaneously with each for the dye suitable for individual components in the presence of 0.1 to 2 g / 1 bath volume a mixture of 35 to 65 parts of an anionic leveling agent, in particular an agent of the general formula R (A) nR ', in which R and R' are the same or different sulfonated benzene or naphthalene rings, A is a radical CH "S02 or NH and n is a integers between 0 and 4 inclusive mean 36 to 65 parts of a weak cationic complexing agent such as polyvinylpyrrolidone or a condensation product from ethylene oxide with a fatty amine with a long chain or an aromatic amine, and 0.1 to 3 parts of thiourea or one of its N-alkyl derivatives, the Total amount of auxiliaries 10 percent by weight of the material to be colored not exceeds, is carried out. This coloring is for products, for example based on mixtures of certain acrylic polymers and polyamides is desirable. The invention allows in particular the simultaneous coloring of two materials, each with the type of dye suitable for it, without precipitation or Flocculation.

It should be mentioned that the cationic or basic dyes for the coloring of products with acidic spots can be used, such as normal acrylic fibers, d. H. based on polymers with a content of at least 85 percent by weight of acrylonitrile, and acrylic fibers with acidic groups, and that the anionic or acidic dyes are suitable for products with basic sites, such as fibers based on polyamides, acrylic fibers with basic Groups, and in the field of natural fibers, silk, sheep hair (wool, mohair), Rabbit hair (angora) etc.

It is therefore known that the coloring of products based on Mixtures that are often found in the textile field, the use of dyes may require belonging to the above two groups, and that the presence of the dyes in question in a common carrier (dye bath, printing ink u. The like.) Precipitation or flocculation phenomena can cause a correct Make staining impossible.

When such phenomena are due to reaction between anionic dyes and cationic dyes occur, the less they are, the more pronounced the carrier is viscous. This makes it easier for these phenomena to occur in a dye bath than in a printing paste in which the presence of thickeners makes them strong belittles.

So far you have worked in two successive stages: Man begins with one of the textile components of the product with the dye or dyes the group that is suitable for him to color and color after this or this Dyes are exhausted, the other component with the dye or dyes the other group. The coloring is done in a single or two baths and mostly in the presence of a generally non-ionic product with a dispersing effect or done otherwise. There was even such a coloration, also in the presence such a means; proposed in a single bath and a single step, but this measure is only applicable to certain well-defined dyes, and the results obtained are due to precipitation and poor abrasion resistance the colorations achieved are not very satisfactory. The inventive method has the advantage of being much more general as it applies to all anionic dyes and allows all cationic dyes to be used and to improve them in a simpler way Results than the known method.

The method according to the invention relates to the coloring of all products, those made from a mixture of textiles with acidic spots and with basic spots consist, at the same time the different components, each one with the dyes that are suitable for him, d. H. using a mixture of dyes with an anionic or acidic character and dyes with a cationic or basic character, in the presence of an anionic leveling agent, one weakly cationic complexing agent and thiourea or one of its N-alkyl substituted derivatives colors. The three additions also allow the evenness to improve and thus without stripes or other defects and in all colors, even very bright to color. They also have the following advantages and effects: Liveliness of the nuances, wash resistance, no oxidation of polymers, no Degradation of colored material, no color irregularity and the like allow them, and this is one of the essential and surprising features of the Invention, the simultaneous presence of acidic and basic dyes Dyes in one and the same carrier without precipitation and without flocculation, which is the There is no need for coloring in two stages and a simplification of the work process and in particular enables a considerable saving of time.

The three additives used and their weight ratios are that the following: 35 to 65 parts of an anionic leveling agent, especially one those of the general formula R (A) n.R ', in which R and R' are the same or different sulfonated benzene or naphthalene rings, A is a radical CH2, SO2 or NH and h is a an integer between 0 and 4 inclusive. (Example: sodium a, rx = dinaphthyl-ß, ß'-disulfonate, Sodiumcc, a'-dinaphthylmethane-ß, ß'-disulfonate or analogues).

36 to 65 parts of a weakly cationic, complex-forming agent, such as polyvinylpyrrolidone or a condensation product of ethylene oxide with a Fatty amine with a long chain or an aromatic amine (examples: fatty amine with 18 carbon atoms, substituted with 6 molecules of ethylene oxide or analogues).

0.1 to 3 parts of thiourea or one of its N-alkyl derivatives, such as for example N-monomethylthiourea; if in the following only from thiourea is mentioned, it should also be understood that it is one of the named Can trade derivatives.

The use of a sulfur containing Reducing agent is particularly known for the treatment of textile products made of polyamides, however, it has now been found that thiourea used with the anionic agent and the cationic agent, in the form of traces in the coloring medium, acts as an antioxidant catalyst behaves.

The following are anionic dyes, especially the usual ones acidic dyes, the acidic metal-containing dyes (1: 1 and 2: 1) or the special ones acidic dyes.

The baths produced are at 20 ° C for a time greater than this Stable for more than 3 to 4 hours and for almost all dyes even more than 24 hours. It was found that even after 72 hours of storage, baths were beginning to show Show flocculation completely and quickly by simply reheating to about 80 ° C can be made homogeneous.

To better understand the technical features and benefits of the present invention are given in the following embodiments. These serve only to explain the method of execution and the applications, without to limit the invention.

The preferred mode of operation of the invention is as follows: One sets a dye bath between ordinary temperature (e.g. 20 ° C) and 100 ° C and preferably at about 40 ° C. The anionic leveling agent is brought into the bath, the cationic complexing agent, thiourea or one of its N-alkyl derivatives a.

The total amount of these three ingredients to be used is from 0.1 to 2 g / 1 bath, without exceeding 10% by weight of the material to be colored. For example, 465 g of sodium x, x'-dinaphthylmethane-ß, ß'-disulfonate, Add 465 g of polyvinylpyrrolidone and 10 g of thiourea.

Adjust the pH of the bath between 2 and 6, and preferably to about 4.5, with acids such as acetic acid, lactic acid, formic acid or sulfuric acid (depending on the desired pH). Then you put the or the previously dissolved dyes belong to one of the two groups. After finished Mixing is used to set the dye or dyes of the other group, which have also previously been dissolved to. It is found that there is no precipitation whatsoever.

The material is at a temperature between ordinary temperature (e.g. 20 ° C) and 60 ° C, preferably at about 40 ° C, and 5 to 10 minutes kept moving. The ratio of material weight to bath volume is 1 / e up to 1/1. The temperature is then increased to 100 ° C. and higher, preferably to about 120 ° C. The upper limit of the temperature varies depending on the dyes and the material to be colored and should be below the value that causes degradation evokes. For silk, for example, it is difficult to exceed 100 ° C, and for certain dyes it is difficult to exceed 130 ° C, while for numerous other 140 ° C can easily be reached. In the following examples the material to be dyed was at temperatures ranging from 100 to 120 ° C, Treated to exhaustion of the baths. In all cases are the colorations achieved excellent even and well differentiated, the abrasion resistance is very good, and there was no deterioration in light resistance, washing resistance and perspiration resistance of the dyes used simultaneously in the present invention compared to those of the dyes used separately.

The method given above was used in the following five examples. In these examples, the percentages are expressed in percent by weight, unless otherwise stated, and for the dyes they are expressed in percent by weight, based on the material to be colored. The names and CI numbers of certain dyes given below are references to the Color Index (2nd edition 1956). EXAMPLE 1 The two components of a fabric are made up of an endless thread based on polyamide 66 in the warp and in the weft of a web of fibers made of copolymers with acidic groups with a content of 940 /, acrylonitrile, the weight ratio of these Ingredients is 70:30 in a single dye bath at 40 ° C. The bath was prepared as follows: In 1000 l of water at 40 ° C., 465 g of sodium x, x = dinaphthylmethane, β'-disulfonate, 465 g of polyvinylpyrrolidone, 10 g of thiourea are introduced. The pH of the bath is adjusted to 6 with acetic acid. Then 10/0 of a previously dissolved kaiionic dye (C.1. Basic Red 29, 50040) is added. After mixing is complete, 10/0 of a previously dissolved customary acidic dye (CI Acid Blue 80, 61585) is added. It is found that there is no precipitation whatsoever.

After the material has been introduced into the bath (the ratio of material weight to bath volume is 1:20) this is kept in motion for 5 to 10 minutes. then the temperature is increased to 120 ° C. and dyeing is carried out at this temperature for 1 hour.

The weft is colored red and the warp blue, the two colors are vivid, very well indistinguishable and firm, even against abrasion. EXAMPLE 2 The two components of a fabric containing, in the warp and in the weft, thread on thread of web of fibers of copolymers with acidic groups containing 940/0 acrylonitrile and wool in the same weight ratio, are dyed in a single bath as in Example 1, with the exception that the temperature 105 ° C, the ratio of material weight to bath volume is 1:50 and the bath contains the following dyes in addition to the auxiliaries: 10 /, the blue cationic dye, CI 50 220, 10/0 of the yellow metal-containing dye (1/1), CI 19 010.

The acrylic fibers take on a beautiful blue color that is completely contrasted with the yellow of the wool.

Example 3 The same procedure is used, but at 100.degree a woven fabric of mixed fabrics Acrylic fibers with acidic Groups and wool in the same weight ratio and the following dyes: 10 /, the yellow basic dye C.I. 48,065, 0.5% of the blue acidic dye C.1. 62105, 0.5% of the yellow acid dye C.I. 18 835, the acrylic fibers with acidic groups turn bright yellow and the wool green, with a very good color Contrast.

EXAMPLE 4 A fabric containing a warp made of spun from normal acrylic fibers and a weft of silk with the same weight ratio of the two components is dyed as in Example 1 with the exception that the temperature 100 ° C, the ratio of material weight to bath volume 1 : 50, the dyeing time is 11 1/2 hours and that the bath contains the following dyes in addition to the auxiliaries: 0.5% of the blue basic dye C.1. 50 306 10/0 of the yellow basic dye, C.1. 48 055, 0.05% of the blue acidic dye CI 61585, 0.6% / a of the brown metal-containing dye (2/1) C.1. 20 018, 0.10 / 0 of the yellow cobalt-containing dye (2/1) C.1. 11650.

The chain turns yellowish-medium green and the weft golden beetle beige. Here, too, the two colors differ noticeably and have emerged strongly. Example s A fabric with a warp of endless thread based on polyamide 11 and a weft of spun fiber made of copolymer with acidic groups with a content of 9411/0 acrylonitrile, the weight ratio being 70:30, is according to Example 1 with colored with the exception that the temperature 120 ° C, the ratio of material weight to bath volume 1:20, the dyeing time 11/2 hours, the polyvinylpyrrolidone is quantitatively replaced by a condensate of 6 moles of ethylene oxide with oleylamine and the bath except for the auxiliaries following Dyes contains: 10/0 of the blue basic dye, CI 50160, 101, of the blue, acidic dye C.1. 42 735. The warp is colored reddish blue and the weft is colored bright blue. The two colors stand out nicely and the tone-on-tone effect is remarkable. In all of these examples it is found that the resistance of the threads or fibers of one category to dyes of the other category is good. This is all the more apparent the more different the colorations are, as is the case in Examples 1 (blue and red), 2 (blue and yellow) and 4 (yellowish-medium green and beige). It should also be mentioned that reservations can be made with a material which is neither colored by the acidic dyes used nor by the basic dyes used. For example, you can dye acrylic fiber with acidic groups red, endless polyamide thread blue (as in Example 1) and reserve continuous thread based on polyester, which could for example be dyed in the mass. It should also be noted that only two types of threads or fibers were used in the examples. However, more than two can be provided, for example acrylic fiber with acidic groups, silk -f- polyamide fiber. It is also possible to use components of the material to be colored that are capable of coloring with both one and the other category of dyes (for example polyvinyl alcohol).

Claims (1)

Claim: Process for dyeing products which simultaneously contain at least one constituent with basic groups and at least one constituent with acidic groups, and in particular textile products using at least one dye with an anionic character and at least one dye with a cationic character, characterized in that dyeing in an aqueous bath at a pH value between 2 and 6 at a temperature of at least 100 ° C simultaneously with each dye suitable for the individual components in the presence of 0.1 to 2 g / 1 bath content of a mixture of 35 to 65 Sharing an anionic leveling agent, in particular an agent of the general formula R (A) nR ', in which R and R' are identical or different sulfonated benzene or naphthalene rings, A is a radical CH2, SO, or NH and n is an integer between 0 and 4, inclusive, mean 36 to 65 parts of a weakly cationic complexing agent such as Polyvi nylpyrrolidone or a condensation product of ethylene oxide with a fatty amine with a long chain or an aromatic amine, and 0.1 to 3 parts of thiourea or one of its N-alkyl derivatives, the total amount of the auxiliaries not exceeding 10 percent by weight of the material to be colored, is carried out.